Azo dyestuffs and process of making same



Patented Aug. 18, 1925 UNITED ATENT OFFICE.)

HERMANN WAGNER, OF HOCHS T-ON-THE-MAIN, GERMANY ATSSIG NOB, BY MESNE AS- SIGNMEN TS, TO GRASSELLI DYESTUFF CORPORATION, OF NEW YORK, N. Y.,. A GOR- v PORATION OF DELAWARE.

azo nynsrnrrs Ann rnocisss or MAKING seam.

Nonrawin Application filed February To all whom it may concern:

Be it. known that I, HERMANN WAGNER, a citizen-of Germany, residing at Hochston-the-Main, Germany, have invented certain new and useful Improvements in Azo Dyestuffs and Processes of Making Same, of which the following is a specification.

In my U. S. patent application Ser. No.

544,613..filed March 17, 1922'has been described a process of preparingparticularly fast azo dyestuffs consisting in the combination of. any diazo components with 2.3-hydroxynaphthoic acid-o-toluidides.

In further developing the inventiv idea set forth'in the said application, of increasing the fastness of the dyestufls in question by introducing methylgroups in ortho-posh tion to the imide group of the 2.3 -hydroxynaphthoic acid arylide, I have found that in an analogous manner there may also be obtained products of excellent properties, particularly of very greatly increased fastness. to kier-boiling, by introducing .alkyloxy-, aryloxy-, and aralkyloxy groups into the'same ortho-position. Besides the good qualities of the products obtainable according tosaid U. S. application Ser. No. 544,613thesebodies also possess a greater fastness to light than the products of the said application.

In all of these combinations of diazo compounds With o-alkyloxy, o-aryloxy, or oaralkyloxyanilides of the 2.3-hydroxynaphthoic acid, those dyestuffs which are halogen-substitutedin the diazo component or in the coupling component, and particularly, thos which are halogen -substituted in both components, are distinguished by their particularly great fastness to kierboiling, which fastness, especially with those t combinations which are halogenated on both sides, is greater than has hitherto been observed with azo dyestufi's By diazo component is meant the diazotlzed amine which is combined with 12, 1923. Serial No. 618,709.

another component called the coupling comporkent 1n the production of the azo dyestu The new dyestuffs have the general formula:

, N=N-R wherein R stands for any residue, X for hydrogen, halogen or any substituent, Y for an alkyloxy, aryloxy or aralkyloxy group in ortho position to the nitrogen.

The azo dyestufi's which can be obtained by combining anydiazo compounds with the 2.3 hydroxynaphthoic acid anilide of the formula:

wherein X stands for halogen and Y for an alkyloxy, aryloxy or aralkyloxy group, have proven to be particularly valuable dyestufi's.

The. combination of the components may, as in the case of said U. S. application Ser. No. 544,613, be efi'ectu'ated either in an aqueous solution, in which case pigment dyestuffs are obtained, or the preparation of these pigments may bej'carried out on the fibre, whereby dyeings of the above. described fastness are obtained. 7

Examples.

made up to 1 litre.

B 65 gr. caustic soda solution 22 Be.

It is then dried and printed with the fol- (5.) The'material is'p added with a solu- 65 v lowing colour: tion of: 18 8L of (imitaumoluidine v 23 grblziil-lygroxynaphthoic acidwy-chloro-o-anisidide (NH.OCH;.

com. 0 we. er

I t t 60 gr. caustic soda solution 22 Be. boiling water 6 I: ccfikagisigrgggglligiirhacld of 22 B. specific gravity, mix well 2, gr Dam p P N I gr. 0 10a, en a i 8 gr. of sodium nitrite dissolved in made up to I hire- 70 50 com. of water I 550 gr. of tragacimth (00:1000) and to this add before use t 1s then dried and printed with the folgr. sodium acetate. l i g colour: 6 Q 1 7 2&7), 5 gr. 4-chl(t ro.-3-to1uidine hydrochloride are dissolved in i coin. wa er (2.) The yarn 1s mpregnated with the 138 com. h glilrochllo'ic acid 22 B., then cool with 75 gr. ice en a followlng preparation i 53 En sodmtm marge, gilssoiyeq in ccm.wa er a w ies imng 12, 7 gr. of 2.3 hydroxynaphthoic acid-o-anisidide 540 gr. tragacai ith 60 1000 and add before use 20 1 com. of caustic soda solution 34 B. 20 gr. sodium acetate core. of sodium-Turkey-red oil Y 15 500 hi if i with id t t t l 1 ew oema eup e0 waer 0 30 fire (6.) The material 1s padded with a solution of: i The lmpregnated y m 1s wrung 1" and 27 gr. 2.3-hydroxynaphthoic acid-5-bromo o-anisidide (NELOCHs dyed with the followlng dlazo solution i 20 gr. caustic sod; solution 22 Be.

14,l gr. of 5-chlor -o-toluidine are dissolved with E para Soap 8 5 24 com. of hy ochloric acid of 22 B6. and made up to mm 4 I i i 200 core. of boiling water, then cooled by adding I I g g; 3% fi' i Siadded wlffle a 9 It -1s then drled and printed wlth the fol- 50 com. of watr. lowing colour: 7 x i T The. solution is made up 7 to 4 litres to 7 g rg g p n i in (OCH3:NHI1C1=1-2-4) which are added 20 gr. sodium acetate, be- 24 com: hydrochloric acid 22 B., mix well toa paste cool with fore usin it f 150 gr. ice, then add V g j 8 gr. sodium nitrite, dissolved in After, dyeing, the material is well wrung- Water p 550 gr. tragacanth 60 z 1000 and add before use 30 out, washed and soaped. 20 gr. sodium acetate The material s padded with a. solu- 1 tionofr i i r p t (7.) The maternal 1s padded with a solu- 20 gr. of 2.3 hydroxynaphthoic acid-o-anisldide t10n Of 2 60 gr. of caustic soda solution 22 Be. 21) gr. of para soap P. N. I I i I 23 gr.C 12.3;lgygiroxynaphthoic aeid-S-ehloro-o-anisidide (NH.OC H3. 35 made up to 1 litre. v 4 65 gr. caustic soda solution 22 B.

20 gr. sodium ricinolate I It is then dried and printed with thefollowing colour:

15, 7 gr. ofp-chloranisidine (OCH:: NH2ICl=1.2.4)

made up to 1 litre.

It is then dried aid printed with the fol- 200 m, of water 1 lowmg colour 24 com. of hydrochloric acid 22 Be.; mix well to a paste and cool with I 15, 7 gr. p-chloroamsidine (OCHa:N Hz:Cl= 1.2.4) are dissolved with 0 150 gr. of ice, then add 24 com. hydrochloric acid 22 B. and I 8 -21. of sodium nitrite, dissolved in I g 200 com. boiling water; cool well and add 60 com. of water 150 gr. ice. Add while well stirring 550 gr. of tragacanth 60 1000 and to this add before use 8 gr. sodium nitrite, dissolved in *20 gr. of sodium acetate v 50 com. water and-make up with water to 45 1 kg. 7 i 500 gr.

(4;) Th t i l i dd d ith a 1 ThlS diazo solut1on 1s thickened with 131011 Of'i' 480 gr. tragacanth 60-1000 and there are added before use p 20 gn'sodmmacetath cryst. 23 gr. 2.3-hydroxynaphtho1c acid-5-chloro-o anisidlde (N H.0OHi. I (lb-1.2.5) 1 kg. 2 1 i 1' wdiumricinfifl 7 L -(8.) The material is padded with a. solu made up-to llitre. tlOn ,Of: It is then drid and printed (with the fOL 23grb1i1h2y5droxynaphthoic acid-Schlormb-anisidide Nrhooni.

lgwing 3010111- 1 65 gr. caustic soda solution 22B I 20 gr. sodium ricinolste 16,8 31'. 4-nltro-o-anisidine are dissolved with l s com. lgoyi'idiigchloiiec acidu22 et andh m 0cm. gwarweoooe wit 150 gr. ice. -There arethen added, whilewell stirring,- It 1s then dried and printed with the follow- 8 gr. sodium nitrite, dissolved in i colour 60 gr. water and the whole is made up with water to r g Y 4 0 5 gmmm I v I 1 17, 5 grgvit-lchloro-z-toluidine or 3-chloro i-toluidine are dissolved I 24 com. hydrochloric acid 22 B6. and

ThlS diazo solution 1s thickened with 200 com. boiling water; cool well and add I P gr. ice. Add while well stirring 480 gr. tragacanth 00:1000 to which are added before use 8 81'. sodium nitrite, dissolved in mgr. sodium acetate cryst. 60 com. water and make up with water to i e. 'WQ.

This diazo-solution is thickened with 480 grhtragacanth 60 $1000 and there are added befor use 4 g gr. sodium acetate cryst.

9.. "The diazb Solution prepared in the usual way from 14, 1 gr. l-ehloro-o-toluidine is run, while stirring, into an aqueous suspension of 20 gr. of 2.3 hydroxynaphthoic Bill . made up to 1 litre.

' lit is then dried and printed with the folacid-o anisidide, made by dissolving it incaustic soda solution and re-precipitating with diluted acetic acid. The dycstufi separates in the form of red flakes. It is then filtered, washed and dried. I I (19.) The material is padded witha solu tion of: 26 gr.2jLi-hvdroxynaphthoicacid-5-chl0ro-2-phenetidide (NH 002KB: 20 gr. pzjd dgli P. N. Q 70 com. caustic soda solution 22 Be.

made up to 1 litre.

It is then dried with the following colour 23g, 5 gr. 2.5-dichlorol-toluidine are well mixed to a paste with com. water and 24 com. hydrochloric acid 22 B.; then cool with -150 gr. ice and add 8 gr. sodium nitrite, dissolved in ccnLwater. I

This diazo solution is thickened with 530 gr. tlragacanth 1000 and add hefore the use of the printing. 3

0 our.

20 gr. sodium acetate 7 1 kg. I 11.

tion of:

23 grb2li-iiggoximaphthoic '.acid-5'chloro-2-anisidide (N H 00113:

20 gr. para soap P. N. com. caustic soda solution 22 Be.

The material is padded with a solulowing colour :Y Y

19, 1 gr. 2.5-dichloro-4-aminoanisol are well mixed to a paste with 200 com. water and t I 24 com. hydrochloric acid 22 B.; then cool with 150 gr. ice and add 8 gr. sodium mtrite, dissolved in 50 com. water. I

4 This diazo solution is thickened with 530 gr. tragacanth 60: 1000 and there are added before using the printed colour i I I 20 gr. sodiumacetate (12.) The material is padded with a solution of: v

24,9grb2l3-{iggoxynaphthoic acid-5-chloro-2-anisidide (NHDCHr com. caustic soda solution 22 Be. 20 "gr. para soap P. N.

Zia ie up tollitre. v It is thendried and printed with the following colour:

Y 10 gr.'p-diaminodiphenylamine 150 gr. ice then add 200 com. hot water and v 24 com. hydrochloric acid 22 B.;-mix well to a paste, cool and add 8 gr. sodium nitrite dissolved in 50 com. water, pour, while stirring, into 3 538 gr. tragacanth 60 1000 and add beforeuse 20 gr. sodium acetate 150 gr. water and 7 0 20 com. hydrochloric acid 22 B.; cool and add dried.

13.) The material is padded with the 65 preparationindicated in Example 12 and printed with the following colour:

. 17,2 gr .fl2i2-dichlorbenzidine hydrochloride are made into a paste W1 v p 150 gr. ice. ,Add, while stirring,

S gr. sodium nitrite dissolved in 50 ccm. water and make up to I This diazo solution is thickened withz I 5 480 gr. tragacanth 60 1000 to which are added before use 20 gr. sodium acetate cryst.

. (14.) The yarn is impregnated with the following preparatlon: i 3

12, 45 z.a l gmx na hthoicacm-ecmomaanisiaide (Nn.ooHt.

27 com. caustic soda solution 34 B. 30 com. sodium Turkey red oil 50% v 500 com. hot water: make up with cold water to j I "I llitre 3 5 The impregnated yarn is wrung out and I dyed with the follow ng dlazo solutionz,

2,82 gr. alpha-naphthylamine base are made to a paste with 53, 4 com. hydrochloric acid 22 B. and with com. water, cooled by adding 25 gr. ice; add whilestirring a solution of 1, 5 gr. sodium nitrite 1n 0 com. water and make up with cold water to 1 litre. Add before use 4 gr. sodium acetate.

Diazo solution.

1, 78 gr. 4-chloro-1-naphthylamine base are dissolved with 00 com. hot water and e 2, 4 com. hydrochloric acid 22 Be. then cooled with 600 gr. cold water and 100 gr. ice, whereupon are added 0,8 gr. sodium nitrite dissolved in com. water and further added before use 2 gr. sodium acetate and made up to 1 litre i The whole is then, as above indicated, poured, while stirring, into:

3, 21 a s-h gm na hthoic acid-5-chloro'2-auisididc (NH.OCH;- 1 16 10, 5 com. caustic soda solution 22 Be. and 124 gr. barytes made up to 1 litre I i Having now described my invention, what. I claim is-:' v I 1. As new products, the azo dyestuffs of the general formula: K

' 4 N-NR wherein R stands for any residue, X foi- -hydrogen,'ha1ogen oriany substituent, Y for an alkyloxy, ary'loxy or aralkyloxygroup v in ortho position to the nitrogen.

5 As new products the azo dyestuffs wherein X stands for halogen and Y for an 15 'Which n e Obtained by combining any a1ky1oxy,'ary1oxy or aralkyloxy group. diazo compounds with the 2.3-hydroxy- In testimony Whereof,I affix my signature.

' naphthoio acid-anilide of the formula: DR. HERMANN WAGNER. i 

